Ploitation s petboliferes



Patented Mar. 8, 1932 "timrsn STATES "PATENr OFFICE ALBERT GODEL, OF PARIS, FRANCE, ASSIGNOR TO SOCIETE DE BECHEBCHES ET I) nx-t PLOITATION S PETRJOLIFEBES, F PARIS, FRANCE, A FRENCH SOGIE'DE ANONYHE PROCESS OF ACTIVATIN G CARBON No Drawing. Application filed December 29, 1927, Serial No. 243,845, and in France January 14, 1927 Numerous processes for the activation of carbon are based upon the treatment of carbonaceous substances by means of gases at high temperature.

These processes difier as regards the particular conditions in which the operation of activation is carried out, so that in the preparation of carbons of the same activity by different methods from the same carbonaceous substance, the yield of active carbon may vary considerably.

The. improvement forming the subjectof the present invention, is applicable in a general manner to all known processes of activation of carbon by gases, whatever be the state of the primary material, that is, whether it be raw, natural or artificial, agglomerated, already carbonized whollyor in part, partially activated or not activated, and so on.

The novel treatment is based upon an impregnation of the product to be activated, the impregnation being carried out with very small doses (1 to 5% under normal conditionsfzl of bases, salts or acids, possessin lireproo ng properties, these substances dieing employed in the pure state or in mixture.

It has already been proposed to use bases, salts or acids, having dehydrating, carbonizing, oxidizing and other actions, of greater or less degree, for the direct activation by carbonizing in closed vessels of raw carbonaceous materials, such as peat, saw-dust, leather waste, etc., but in all cases without the aid of activating. gases, for the activating action was due to the bases, salts or acids, and not to gases.

Such processes are applicable only to raw or incompletely carbonized primary materials, since the chemical agents utilized operate mainly during carbonization and would not produce any efiect upon products already carbonized in the ordinary manner.

Moreover, these processes'require a high proportion of the chemical agent used for activating (for example to 1 O0 er cent) in order to produce an appreciab e activation; doses ,as low as those mentioned above would not give any appreciable activation.

There has also been suggested the use of certain acids, bases or salts, with a view to tion.

the activation of materials already coked, but

the suggestion did not reach an industrial application because it was due to a complete misunderstanding of the causes of the phenomenon observed. 'As a matter of fact, it is practically impossible to avoid the entrance of air or of burnt gases at high temperature into the retorts; for the latter are often porous or imperfectly gas-tight at red heat, so that the very feeble activation observed in that case must be attributed mainly to such gases and not to the action of the chemical agents upon the carbonaceous matter; assum ing it to be a fact that the latter had been completely carbonized prior to the use of the chemical actifying agent.

Moreover, it is known to iriix more or less intimately with the carbonaceous matter, such substances as lime, carbonate of magnesia, volatile chlorides etc., intended to evolve activating gases, like carbonic acid gas, chlorine, and in some cases oxygen, which assist the activation, in combination with activating gases which can be introduced in addition into the retorts. These substances are likewise employed in fairly large proportions, 50 to 100 per cent, and they serve also as spacing agents to help the activation.

From the foregoin statements, it can readily be understoo that the chemical agents utilized hitherto for the activation of carbon, with or without the aid of a'ses, have an action totally difierent from t at sought in the present invention.

I have observed that slight traces of various impurities in the primar carbonaceous matter are capable of modi ying considerably its activation by the gases; these impurities, forexample in the case of wood, charcoal, etc., are constituted by ashes which have an important influence upon the said activa- The present improvement consists then in incorporating in the material, previous to its activation or in the courseof the activation, a suitable but always very low proportion of a suitable impregnating agent, for example by macerating the charcoal in. a titrated solution of the substance selected, or else by introducing the said substance either in the dry and pulverulent state, or in the liquid state, atomized or not, into the mass of carbon, for example in the course of the treatment of agglomeration.

Thus, there will be obtained according to the present invention an active carbon, excellent for the absorption of gases byimpregs nating wood charcoal, in natural granules or artifically agglomerated, with an agent'com si sti fiof phosphoric acid, .boric acid, boratc o s caustic soda, alkali phosphates, silicate oi soda, etc., this carbon being subjected after drying to a treatment of activation by activating' gases at high temperature. 4

1 a iven activity, the product above mentions Will be denser, harder, less black andlesfs friable than the product obtained wigiout the preliminary impregnation.

ccordin to ex eriments carried out, it seems that t e action of certain impregnating agents in theactivation of carbon must be attributed to their more or less fire-proofing properties, the bodies capable of giving rise t0 filSible compounds at the activation temperature appearin to assist the activation as re ards yield and t e properties generally required'for the absor tion of ases.

The action of the re-prooiin'g agents might be exp'lainedin the following manner;

Certain; inactive carbons, wood charcoal for example, may be considered as constituted by e a skeleton of active carbon, ofwhich the capillarV Pores are saturated with tars or heavy 33 hydrocarbons evolvedduring the carhonization ofthe wood. The processes of activation by gases have for effect to destroy these tars 01$ hydrocarbons by selective oxidation while leaving intact the skeleton of active carbon.

In practice, however great the care taken in thactivatiomjthere is inevitably a destru'cf tion or a part of the active carbon by combus Now, if the carbon is first impregnatledwith a substancetusible. at the activation temperature, it can easily be uhderstood that thissubstance penetrates, throughout thefree active carbon, and" that the fused material is the more thoroughly absorbed hy -the particles of carbon in proportion as the latter are more active, On the contrary, the'inactive particles of carbon, the hydrocarbons of the charcoal,

etc'. are not moistened or im' re nated by the fused substance when ignite I ';'t ose particles are left freely exposed'to the oxidizing action of the gases,'whereas the active carbon is protected. I Another phenomenon can likewise take lace if the material to be activated is slight- CD y heterogeneous, like wood charcoal for ex: ample, of which the sap wood issofter and more rapidly activated than the heart wood;

' thesofit and generally spongypart will retain a. higher proportion of theimpregnating sub nce h en t aa, so h y PIT-$1.-

., carbonate of soda, bisulphate of soda tection of the soft parts there will be obtained a regularization of the speed of activation consequently an improvement in the yield.

Thus, in the application ofthe invention, success hasbeen obtained in activating with an excellent ield the waste or powder of wdqdcharcoa? with all the processes now in usesuc an operation could not be carriedout profitably owing to the variety of the nature of the tragumnts of carbon, which are constituted sometimes by the bark, sometimes by the sap wood and sometimes by the heart-wood.

It ma be noted that it is impossible to interpret he action of the impregnating agents mentioned as an action of transitory oxidation,theim re natin a cut 1a in always g g P y e the part 0 inermediary between the previously carbonized charcoal which would be oxidized While being activated by contact, and the gases which would regenerate the inipregnating agent by oxidation; in fact the same impregnating substances employed even in strong doses but without the assistance of activating gases are absolutely without any action, although they'may be for example of an oxidizing nature, like phosphoric acid. On the contrary, if the operation is carried out in an atmosphere of activating gases, phosphoric acid employed even in very small doses increases the yields and the activities because it is of a fire-proofing nature.

The fire-proofing properties of certain stances have already been utilized in the car bonizing of organic materials with a view to obtaining incombustible carbon (see French patent specification No. 162,282, filed May 21st 1884).

It has also been pro osed to impregnate active carbon with small quantities of phosphoric acid in order to render it incombustible (see German patent specification No. 374,208, filed September 6th 1921), but it is to be noted that the impregnation of the carbon has never been utilized'hithe-rto for the manufactureof active carbon.

The impregnation of carbonaceous substances in accordance with the invention can be carried out invarious Ways.

There has been mentioned above the macoration of the carbon in a titrated aqueous solution of the impregnating substance; the operation may'likewise be carried out in the manner indicated hereafter, which will be 'particularly applicable in the preparation ofmoulded active carbons intended for the absorption of gases;

The carbonto beagglomerated (active or inactive) is ground'to an impalpable powder which is then mixed up with a binder, such as sugar, bisulphite cellulose-liquor, coal tar, woodtar, oxidized tars, dextrine, algine, gum arabic, iron. gels, alumina, sulphate of lime, ctc., according to the methods practised in the agglomerated coalindustigy v Moreover, and in accordance with the invention, there is incorporated with the paste a small proportion of the fire-proofin bodies already mentioned; phosphoric aci boric propertes still further if necessary, the fol lowing procedure may be adopted .Carbon, impregnated or agglomerated with organic substances, and coked by the usual known methods, with or without addition of the impregnated substance, will be ground up into an impalpable powder; this powder, after the second pulverization, will have a greater density than that obtained from the initial carbon and will be employed advantageously for the preparation of fresh agglomerates, with or without addition of impregnating substances; the dried, calcined and activated agglomerates, coated if necessary by known processes, will constitute a carbon of very high density and strength. I

In all cases there may naturally be adopted measures for eliminating ashes from the carbon by washings after activation; this will not always be necessary in view ofthe small proportion of impregnating substances utilized.

lVhat I claim is 1. In the preparation of carbon to be activated bymeans of gases, the steps of subjecting the material, to an impregnation with not more than 5% in dry 'weight of fireproofing substance, and subsequently activating the impregnated material by heating and oxidizing by means of gases at high temperature.

2. In the preparation of agglomeratedcarbon to be activated by means of gases, the step of agglomerating and simultaneously impregnating the material with. from 1% to 5% in dry weight of a fire-proofing agent, and subsequently heating said material by means of activating gases at high temperature.

3. Process for the preparation of agglomerated absorbent carbon, comprising the steps of grinding the material to be activated into an impalpable powder, mixing saidvalue due to its great.

not, and subjecting thesame to treatment by activating gases at high temperature.

4. Process for the preparation of agglomerated absorbent carbon, comprising the steps of grinding the material to be activated into an impalpable powder, mixing said powder with a binder to form an agglomerated paste, impregnating said paste with not more than 5% in dry weight of a fireproofing agent, molding said paste, drying, calcining the molded product, grinding said calcined product into an impal able powder, mixing said powder witha binder to form a second agglomerated paste, molding said second paste, drying and calcining sald second molded product, and subjecting the same to a treatment by activating gases at high temperature.

5. Process for the preparation of agglomerated absorbent carbon, comprising the steps of grinding the material to be activated into an impalgable powder, mixin said powder with a inder to form an agg omerated paste, molding said paste, drying, calcining the molded product, grinding said calcined product into an impalpable powder,

mixing said powder with a binder to form I a second agglomerated paste, impregnating one of said agglomerated pastes with not more than 5%'1n dry weight of-a fire-proofing agent, molding said second paste drying said second molded product, and subjecting the same to a treatment by activating gases at high temperature.

6. In the cou'rseof the preparation of carbonaceous material to be activated by means of gases, the step of subjecting the material to an impregnation'with from 1% to 5% in dry weight of fire-proofing substance, the, impregnated materlal being subsequently carbonized and activated by oxidizing gases 1 at high temperature.

In testimony whereof I hereunto aflix my signature. I ALBERT GODEL.

powder with a binder to form an agglomerated paste, impregnating said paste with not more than 5% in dry weight of a fireproofing agent, moulding the impregnated paste, drying, calcining the moulded prod- 

